Preparation of aliphatic-aromatic



Reiuuecl Sept. 26, 1944 PREPARATION OF AIJPHATIC-ABJOMATIC SULPHONATESRobert Louis Brandt, New York, N. Y., asslgnor to Colgate-Palmolive-PeetCompany, Jersey City, N. 1., a'corporationof Delaware No Drawing.Original No. 2,244,512, dated June 3, 1941, Serial No. 259,792, March 4,1939. Application for reissue May 30, 1942, Serial No.

19 Claims. (Cl. 260-505) This invention relates to the preparation ofcertain improved organic sulphonates and more a solvent comprisingsulphur dioxide.

Among the many classes of organic sulphonates, it has been found thatlong-chain aliphatic substituted aromatic sulphonic acids are especiallydesirable for many purposes because of their stability and unusuallyhigh wetting, washing, penetrating, solubilizing, and emulsifyingefilciency. Numerous patents have been issued on the preparation ofcompositions employing various members of this class.

In spite of the fact that many of the substances possess properties notequaled by any of the other organic detergents, their commercialproduction entails a great many difficulties which not only cause theformation of materials of inferior quality as'to color, odor, purity,uniform ity, general appearance and efficiency, but which also make thecost of production of these materials so high that their salecompetitively with the ordinary soaps and other organic sulphonates ismaterially impaired.

The preferred aliphatic substituted aromatic compounds to be sulphonatedas well as the resulting sulphonates are high molecular weight compoundsand hence it is very difficult to cause the raw materials to react atall and even more difllcult to obtain'substantial yields or anyuniformity of products. If heat is used to speed the reaction and torender the molecule more mobile, some increase of reactivity isobserved, but many side reactions also may occur and impure, nonuniformproducts of inferior color and odor result. Polymerization, oxidation,charring, decomposition, improper substitution, and other difllcultycontrollable and generally undesirable reactions may take place. Theviscosity or plasticity of the reaction mass is so high that mixing ispractically impossible, hence the special equipment necessary as well asthe great amount of energy required to eflfect mixing often renders thecost of manufacture prohibitive. The improper .tions, particularly thesulphonatlon reaction, in a solvent comprising liquid sulphur dioxide.

Liquid sulphur dioxide in such solvent compositions serves severalfunctions in the preparation of these substances which functions are notobtainable with any other organic or inorganic liquid.

Liquid sulphur dioxide is a more universal solvent for the reactants andproducts in reactions of this type. It is a very good solvent forsulphonating agents without materially altering their identity oroperation. Other solvents, such as short-chain oleflnic compounds, whichdo dissolve a sulphonating agent, such as sulphur trioxide, react withthe agent to change its identity, for example, forming carbyl sulphates.Furthermore, if the selected liquid does dissolve the sulphonatingagent, it often does not dissolve the materials to be treated. On theother hand, a solvent for the organic constituents is generally not asolvent for the sulphonating agent or it reacts therewith. If thesolvent does not hold all the constituents in solution during thereaction, a two-phase mixture would occur with possible resultingnon-uniformity of product.

Liquid sulphur dioxide is unusual in that it is generall a solvent forthe aliphatic substituted aromatic compounds as well as for the mixtureof aromatic compounds and aliphatic compounds used in preparing saidaliphatic substituted aromatic. compounds. It is also a solvent for themetal halide catalysts and for the sulphonating mixing results inlocalized over-heating and overv reaction in various parts of thereaction mass and substantially no change in others. Cooling, direct orindirect, is likewise not eflective because of the high viscosity of themass.

This applicant has now discovered that it is possible to commerciallyprepare uniform aliphatic substituted aromatic sulphonates of good odor,color, purity and other desirable properties on an economical basis byconducting the reacagcnts used to preparethe sulphonic acid produc s.

Because of the solvent action of the liquid sulphur dioxide, a singlephase reaction takes place; furthermore the viscosity of the mass may bevaried at will so that through mixing a high degree of turbulence may beimparted to the solution. Thus, temperature control, either direct orindirect, is easily eil'ected.

Liquid sulphur dioxide, because of its low boiling point, is veryeffective as a refrigerant. A portion of the liquid may be evaporated toabsorb the heat of vaporization thereof from the reaction mixture andthus effectively to refrigerate it. The normal boiling point of thissolvent is nearer to the optimum reaction temperature than most of thegenerally used organic liquids, and its low sulphur dioxide appears toform loose addition products with certain of the reagents, and this, inall probability, alters their relative reactivity. This solvolyticproperty of liquid sulphur dioxide for this purpose is unique.

The low boiling point of the liquid sulphur dioxide renders it arelatively simple matter to remove the excess solvent from the finalproduct.

The liquid sulphur dioxide serves another novel purpose by reason of thefact that it has a low solubility in dilute sulphuric acid. The reactionmass containing the excess liquid sulphur dioxide may be diluted withwater to stop the reaction and to cause the mixture to separate intoseveral layers; in the case of two layers, one comprising the aqueouslayer of sulphuric acid and organic derivatives thereof, and the othercomprising the liquid sulphur dioxide and water-insoluble organiccompounds. By control of the amount of water added, even three layersmay be formed; a lower layer of dilute sulphuric acid, a middle layer ofsulphonic-sulphuric acids, and an upper layer of a solution of liquidsulphur dioxide and unreacted organic compounds. Without the liquidsulphur dioxide present, there is a tendency to emulsify thewater-insoluble products into the aqueous layer.

Liquid sulphur dioxide is chemically stable, non-inflammable, and hashighly desirable thermal and heat transfer properties. These propertiesadd to general case of handling at low temperatures and give itadvantages over all previously employed solvents.

The preparation of these compounds is varied but in; general it coversthe substitution of an aliphatic radical in an aromatic nucleus and thesulphonation of the substituted aromatic compound. The reactions may beconducted simultaneously or in the two stages indicated.

The'substitution of the aromatic compound by the aliphatic radical isusually carried out by the Friedel-Crafts reaction modified generally byone o! the important features of this invention of conducting thereaction in a solvent usually comprising liquid sulphur dioxide.Catalysts for this reaction are employed, among which are theacid-reacting metal halides including aluminum chloride, boron fluoride,and the chlorides of iron, zinc, antimony, boron, tin, titanium, indium,as well as the bromides and other halides of'these metals and mixturesthereof; activated tion include benzene, toluene, xylene, cumene,

cymene, ethyl-benzene, naphthalene, diphenyl, acenaphthene,phenanthrene, anthracene, methyl naphthalene, ethyl naphthalene, tetrahydronaphthalene, trlphenylmethane, diphenyl methane, fluorene, styrene,indene, coumarone, solvent naphthas and selective solvent extracts orfractions thereof from coal distillation, Edeleanu or other solventextract of mineral oils containing aromatic constituents, benzylchloride,

phenanthrone, acetophenone, diphenylketone, diphenyloxide, veratrole,benzyl alcohol, phenols. allaylol phenols, hydroquinone, and resorcinol,as well as other agents which function similarly to aromatic compoundssuch as furfural, koiic acid and cyclopentadienes. It is also possibleto employ the various halogen derivatives of these materials.

The aliphatic compounds which may be employed for reacting with thearomatic compounds include aliphatic halides, oleflnic compounds andaliphatic alcohols. These compounds may have one or more operativegroups so that monoor poly-aromatic substitution takes place. wise, thearomatic compound may be substituted by one or more of the same ordifferent aliphatic compounds. Although all aliphatic compounds of theabove classes will operate, it is preferred to employ the long-chain (6'carbon atoms or more) aliphatic compounds. The oleiines which may beused alone or in combination include hexene, heptene, octene, nonene,decene (di-isoamylene), undecene, and so forth, through tetradecene,hexadeoene, octadecene, cerotene and higher oleflnes, as well as thecyclic olefines such as cyclohexene. The source of the oleilnes isimmaterial and includes oleiines prepared by cracking petroleum;polymerizing shorter chain olefinesv such as 'isobutylene, isoamylene,etc.; catalytic dehydrogenation of saturated petroleum or otherhydrocarbons; halogenation of aliphatic hydrocarbons anddehydrohalogenation; and those prepared by dehydrating one or morelong-chain alcohols (branched or straight chain), including hexyl,heptyl, octyl, nonyl, decyl, dodecyl, myristyl, cetyl. octadecyl, oleyl,montanyl, carnaubyl, octadecandiol, ceryl, cyclohexyl, methylcyclohexyl, and melissyl alcohols, and mixtures containing thesealcohols such as those prepared by hydrogenating coconut oil. cocoabutter, soy bean oil, tallow, cottonseed oil, olive oil, castor oil,palm oil, fish oil, whale oil, tall oil, carnauba wax, Japan wax,Chinese wax, montan wax, ceresine, ozocerite, stearone, laurone, and thelike. The liberation of water from the alcohol to form olefines may beeffected by the action of chemical agents or according to catalyticmethods, for example, by means of concentrated phosphoric acid oractivated carbon impregnated with phosphoric acid, phosphorouspentoxide, aluminum oxide, bauxite and agents acting in the same manner.The above listed alcohols may be used directly in the process ifsuflicient dehydrating agents, e. g. of the type of oleum, aceticanhydride, and like agents, are present.

Suitable raw material for the preparation of olefines by the aboveprocedures are the liquid to solid paraflin hydrocarbons of any originsuch as those obtained from mineral oils, petroleum jelly, liquidpetrolatum, or wax, or by distillation of tar, mineral or schist oils;the hydrocarbons which may be obtained by the cracking, reduction orhydrogenation of mineral oils, tars, cracking or polymerizationresidues, or the oxides of carbon; olefinic products of high molecularweight prepared by polymerization by means of peroxides, acids,acid-reacting metal halides, light, or

electric currents; as well as from organic materials of vegetableOrigin, ceresine, ozocerite, lignite wax, brown coal, tar wax, mineraloils such as spindle, and other lubricating oils and their fractions.

It is possible to eii'ect the dehydrogenation by Likecracking the rawmaterial or by introducing halogen and then treating at an elevatedtemperature with formation of the hydro-halogen acid. The freeing of thehalogen is effected by means'of alkali (caustic soda), aluminum oxide,bauxite, zinc chloride, barium chloride and similar agents.

It is also possible to use the halogenated hydrocarbons (preferablycontaining at least six carbon atoms) directly. These compounds may beprepared according to any known procedure from aliphatic compounds ormixtures composed in the major portion of such materials. Suitablestarting materials include the liquid, semi-solid or solid, saturated orunsaturated, hydrocarbons of any origin, having a boiling pointpreferably above 100 0., such as those obtained by fractionating mineraloils as petroleum, tar, coal tar or lignite oils; petrolatum, paraffinwax and the like.

Halogenation of these hydrocarbons may be carried out at ordinary orraised temperatures, the action of light or of halogenation catalystssuch as antimony pentachloride, phosphorous pentachloride, ferricchloride, ferric iodide, and so forth, frequently having afavorableefl'ect on the reaction. Unsaturated hydrocarbons may behydrohalogenated to form the corresponding saturated halogenderivatives. As a general rule in the preparation of mono-arylsubstituted aliphatic compounds, it is advantageous to regulate theproportion of halogen used in such a way that for each gram molecule ofhydrocarbon there will be one gram atom or less of the halogen, thenonhalogenated part of the hydrocarbon serving as diluent in the finalcondensation. It is also possible before halogenation to mix thealiphatic and aromatic compounds used as initial reactants, thealiphatic fractions and/or the aromatic fractions being halogenated inaccordance with the operating conditions. Individual aliphatic halidesmay be employed as, for example, dodecyl chloride, octyl bromide,octadecyl chloride, tetradecyl chloride (branch and straight chained)and related substances.

For aliphatic compounds having more than one aromatic substitution, thealiphatic compound should have more than one functional radical of thegroup comprising halides, olefine linkages and hydroxy groups.For-example, octadecenyl chloride, octadec-diene, octadecenyl alcohol,octadecandiol, dichlor-octadecane, dichlorododecane and the like. If itis desired to prepare compounds having halogen constituents remaining inthe final products, it is preferred not to employ a catalyst of the typeof acid-reacting metal halides. For example sulphuric acid derivativesserve as catalysts for the alkylation of aromatics withhalogen-containing olefines or halogen containing alcohols withoutremoving the halogen from the alkyl chain.

Other substituted aliphatic compounds may be used such as halogenatedfatty acids, hydroxyfatty acids, and-monoand poly-olefinic fatty acidsincluding oleic acid, monochloropalmitic acid, linoleic acid,dichlorostearic acid, and ricinoleic acid; ethers and esters such aslauroyl glycerine monochlorhydrin, tetraethylene glycol. ethyl oleate,ethyl ether of octadecenyl alcohol, dodecyl ester of chloracetic acid;ketonic compounds such as dichlorlaurone; and the like.

It is also possible to prepare acylated derivatives of the aromaticcompound. For example, an acid halide of a carboxylic acid such asbenzoyl chloride, stearoyl chloride, palmitoyl chloride,

lauroyl chloride, myristoyl chloride, caproyl chloride, and capryllicchloride may be reacted in liquid sulphur dioxide and/or other solventswith the aromatic compounds listed above to form'the acylated derivativethereof. 1

The sulphonation, alkylation and acylation reactions are conducted in asolvent, and it is at times advantageous to use a mixture of solvents toimprove the solubility'of some of the organic constituents. Among suchsolvents, in addition to liquid sulphur dioxide, are benzol and otheraromatic compounds; methane, ethane, pentane, butane, propane, and otheralkanes; ethylene, and other oleflnes; petroleum ether; dioxane, diethylether and other ethers; carbon disulphide; carbon dioxide; carbontetrachloride, chloroform, dichlorethane, trichlorethylene,dichlorethylene, dichloro-difluonnethane (Freon) and other halogenatedhydrocarbons; and various mixtures thereof.

It is sometimes desirable to conduct the aliphatic substitution of thearomatic compound in other solvents than liquid sulphur dioxide and thento sulphonate in the presence of liquid sulphur dioxide, with or withoutthe solvent used in the first step. In such cases, the liquid sulphurdioxide may be added to the aliphatic substituted aromatic materialdirectly or along with the suliphonating agent, or both. In preparingthe solutions, it is often advisabletn dissolve the arcmatic constituentalong with or prior to the aliphatic constituent, in view of the generalsuperior solubility of the aromatic constituents. The order ofintroducing the agents may be varied more or less. For example, thesulphonating agent or solution thereof may be added to a solution of thealiphatic substituted aromatic compounds. On the other hand, thealiphatic substituted aromatic material per se or in solution, may beadded to a solution of the sulphonating agent. Solutions of both mayalso be simultaneously brought into confluence, which is advantageous ina continuous process.

Cooling in the varied reactions may be obtained by evaporating a portionbut not all of the solvent used in conducting these reactions. Bysuitable selection of the proper solvent combination, pressure control,and the like. it is possible to obtain practically any desiredtemperature. In addition, refrigeration may be obtained by indirectcooling or by means of other inert refrigerants such as non-gaseouscarbon dioxide added directly to the reacting mixture. Theserefrigerants may be separated and recovered by fractional distillationand compression.

The aliphatic substituted aromatic product may be sulphonatedsimultaneously with its formation, or subsequently, either directly orafter previous elimination of the non-condensed aliphatic or aromaticconstituents. After elimination of the catalyst it is possible, if.desired, to purify the condensation product by distillation or the like.

The sulphonation treatment is conducted while the materials aresubstantially in solution in a solvent comprising liquid sulphur dioxideby means of concentrated sulphuric acid, fuming sulphuric acid, oleum,sulphonyl chloride, sulphur dioxide and chlorine gas, sulphur trioxide,acetyl sulphuric acid, bromsulphonic acid, chlorsuliphonic acid, ortheir mixtures, with or without sulphonation assistants, as for example,agents capable of combining with water, such as acetic anhydride,glacial acetic acid, acetyl chloride, propionic anhydride, butyricanhydride,

phosphorous pentoxide, phosphoric oxychloride, boric anhydride, and thelike. Liquid sulphur dioxide and/or other solvents such as dioxane maybe added to the sulphonating agent before the reaction. The temperatureused varies within wide limits preferably between 15' C. and +15 0.depending on the strength oi the sulphonating agents, the solventcombination employed, and the nature of the material to be sulphonated.It is possible to introduce one or more suiphonic acid groups dependingon the desired properties oi the ilnal products. v

The sulphonation reaction may be stopped by the addition water to thereaction mass, thus reducing the acid concentration. This addition ofwater generates heat which may be used to advantage in removing theliquid sulphur dioxide or other solvent. 0n the other hand, the additionof water may be made under suitable conditions or cooling and/orpressure so that the liquid sulphur dioxide is not vaporised and two orthree immiscible layers are formed, depending on the degree of dilutionwith water. The aqueous layer will contain sulphuric acid or derivativesthereof, and the upper or liquid sulphur dioxide layer will contain thenon-sulphonated material. In a two-layer system the sulphonic acids willbe in the aqueous layer, whereas in the three-layer system the sulphonicacids will be in an intermediate layer. These layers may be separatedand the liquid sulphur dioxide solution'separated into its constituentsor re-used in the sulphonation step. The aqueous solution of sulphuricand sulphonic acids from either source of separation may be extractedwith a relatively concentrated solution of sodium chloride alsocontaining sodium acid sulphate. This step removes a substantialproportion of the excess sulphuric acid from the organic sulphonicacids. The organic sulphonic acids, with or without the excess sulphuricacid, may be neutralized with organic or inorganic bases, as for examplesoda ash. caustic soda. caustic potash, ammonia, methyl amines, ethylamines, butyl amines, mono-, di-, or tri-ethanol amine, mono-, di-. ortri-glycerol amine, pyridine, piperidine, lime, and the like. Othersalts which may be formed include those of magnesium, mercury, lithium,and so on. It is also possible to prepare inorganic salt free materialby preparing the calcium salt, thus causing a precipitation of asubstantial portion of the suiphuric acid as insoluble calcium sulphatewhich may be separated from the soluble calcium salt of the organicsulphonlc acids.

Another way of preparing the inorganic salt free material is to extractthe solid salts or aqueous solutions of mixtures of the soluble saltswith a solvent such as ethyl alcohol, dioxane, acetone, Cellosolve,butyl alcohol, and the like. The'in dividuai salts may be prepared bysalt interchange between concentrated solutions 01' soluble inorganicsalts oi the cation desired with solutions of the organic sulphonic acidsalts on hand. 1

The following examples are given for the purpose of illustrating thepresent invention, but are not intended to be limiting on the scopethereoi:

Example I 360 parts 01' dodecyl chloride. are dissolved in a'mixture of200 parts benzene and 1500 parts a of liquid sulphur dioxide, held in ajacketed auto- -zclave, provided with a stirring device. 200 parts sansof anhydrous aluminum chloride are added, with stirring, in smallportions over a period of about 10 minutes. The mixture is stirred for 4hours. To this reaction product is then slowly added, with vogorousagitation, about 500 parts of oleum dissolved in 500 parts of liquidsulphur dioxide. Temperature control is maintained by circulating acooling fluid through the jacket of the autoclave. The temperature ismaintained at not greater than +5 0. for about an hour, meanwhilecontinuing the agitation. The reaction mixture is now slowly added toice-water. The heat generated by the dilution oi the acid mixture isdissipated largely by the evaporation of the liquid sulphur dioxide,which in turn prevents the temperature from increasing to an undesirabledegree (not higher than C.) while dried on soap-drying rolls.

in 135 parts of liquid sulphur dioxide.

Example II 64 parts of naphthalene and '70 parts of diiso-amylene aredissolved in 700 parts of liquid sulphur dioxide. 74 parts of anhydrousaluminum chloride are added in portions to the' solution during 10minutes. The mixture is stirred for 2 hours, and then there is addedthereto a solution comprising parts of sulphur trioxide Agitation iscontinued for another 20 minutes, meanwhile holding the temperaturebelow 10 C. The reaction mixture is then slowly added to ice-water, withagitation. The heat of dilution vaporizes a large portion of the liquidsulphur dioxide. The last parts or sulphur dioxide are removed byboiling the acid solution for a brief period. The product is washed withethyl ether, neutralized with ammonia,v and extracted with isopropylalcohol to yield an ammonium salt of the aliphatic substituted aromaticsulphonic acid (free of ammonium sulphate). The product is dried byspraying in the presence of an excess oi ammonia gas to prevent firehazard.

Example III 160 parts of diphenyl are dissolved in 500 parts ofdichlorethane. To this mixture is then added 200 parts of a iractionboiling between about 150 C. and 200 C. or a liquid sulphur dioxideextract of a cracked Pennsylvania (aliphatic) mineral oil distillate.parts of 96% sulphuric acid are slowly added with continuous stirring.The mixture is heated to about 5045 C. for about 3 hours, meanwhilecontinuing the stirring. 250 parts of 65% oleum dissolved in 500 partsof liquid sulphur dioxide are then added to the cooled reaction mixtureand stirred for 1 hour at +5 C. Sumcient ice-water is then slowly added,with some external cooling, meanwhile maintaining the pressure on thesystem,

thus causing the mixture to separate into three layers. The solventlayer and the lower weak sulphuric acid layer are separately removed.The middle layer of sulphonic acids is washed twice with liquid sulphurdioxide to extract substantially all of the remaining sulphonatedmaterial. The sulphonic acid layer, after removal from the liquidsulphur dioxide wash layers, is heated to expel the remaining sulphurdioxide. The sulphonic acid solution is then washed with a concentratedsolution of sodium chloride containing sodium acid sulphate to removesubstantially all the sulphuric acid dissolved therein. The remainingaqueous solution of alkyl substituted diphenyl sulphonic acids isneutralized with soda ash. The aqueous solution thereof containing somefree sodium carbonate is spraydried in a spray-tower with hot gases, thesodium carbonate serving to prevent fire in the spray-tower.

The above examples merely show a few of the specific embodiments of thebroad invention given in detail hereinbefore.

The products obtained in accordance with the present invention, eitheras acids or salts, have good wetting, solubilizing, deterging, sudsing,water-softening, dispersing, emulsifying, penetrating, and equalizingproperties. Since their calcium and magnesium salts are water-soluble,they operate efficiently in hard as well as in soft water. They are goodwetting agents both in hot and cold baths, and function effectively inthe presence of large quantities of inorganic salts.

Although the new materials possess unusual deterging, sudsing, andwater-softening properties by themselves, their action may be augmentedby the addition of any of the common auxiliary agents used in soap anddetergent compositions. Suitable addition agents are other emulsifyingagents including soaps, rosinates, long-chain alcohol sulphates,monoglyceride monosulphates, sulphonated mineral oil extracts, turkeyred oil, lecithin, glycerolamines, diethanolamine and triethanolamineand their soaps; alakine soap builders such as sodium carbonate, sodiumsilicate, sodium phosphate, and borax; coloring matter such as dyes,lakes, pigments; abrasives and fillers such as silica, pumice, feldspar,precipitated chalk, infusorial earth, bentonite, talc, starch, and air;liquids including carbon tetrachloride, perchlorethylene,trichlorethylene, glycerine, ethyl alcohol, glycol, tetrahydrofurfurylalcohol, phenol, cyclohexanol, water, tetralin, pine oil, mineral oil,mineral oil extracts, and naphtha; perfumes and deodorants; fats, oils,fatty acids, monoglycerides, vitamins, waxes, gums, or glue; resins;germicides such as phenol, mercury chloride, phenyl mercury nitrate,phenyl mercury chloride, methyl ester of hydroxy benzoic acid, andmercuric chloride; styptlcs such as aluminum chloride and cephalin; anyof the common water-soluble salts such as sodium sulphate, chloride,acetate, bicarbonate, sesquicarbonate, hypochlorite, thiosulphate,hydrosulphite, and hyposulphate, or the corresponding ammonium andpotassium alts thereof. The type of addition agent to be used, ofcourse, will depend on the ultimate use of the new composition.

The water-soluble, water-softening phosphorous compounds of the type oftetraphosphoric, pyrophosphoric or hexametaphosphoric acid and theiralkali metal, ammonia, and amine salts or alkyl esters may also be addedto these compositions.

The final composition, with or without one or more addition agents, maybe formed into beads, flakes, bars, chips, crystals, powders, solutions,liquid or plastic emulsions, pastes, creams, salves, or any other formsdesired. The ingredients may be mixed by any of the common methods suchas grinding, stirring, kneading, crutching, fusing, and drying, byrolls, spray or otherwise, of mixed solutions.

Although the specific examples given hereinbefore indicate a batchprocedure, it is possible to conduct the entire process in a continuousmanner. For example, the aromatic and olefinic compounds may be mixedwith a solvent and then brought into confluence with a liquid sulphurdioxide solution of a sulphuric acid derivative sufilcient to at leastcause alkylation, meanwhile continuously flowing the' materials throughheat-exchangers. At several points in the fiow, additional sulphuricacid derivative solution may be added to complete alkylation and/orsulphonation of the material. Water may be added and sulphur dioxideremoved by heat and release of pressure. The neutralization may beconducted by continuously bringing solutions of the acid or acids intoconfluence with concentrated alkali. The various washing steps indicatedhereinbefore may be conducted by countercurrent flow through suitabletowers at the appropriate point or points in the process. Additionagents, preferabiy in the form of their solutions, may be continuouslyintroduced into the sulphonate solution either before, during or afterthe neutralization. The solution of material, in a continuous manner,may be raised to an elevated temperature to destroy any unstablecompounds and may be concentrated by flash-distillation, which alsoremoves volatile impurities in the product along with the steam.

The compositions may be used in various ways such as washingcompositions for wood, metal, stone, glass, brick, masonry and paintedsurfaces; insecticides; cements; abrasive compositions;

antlseptics; water-softeners; deodorants and disinfectants; water paintsand polishes; sizes, glues and adhesives such as shellac and caseincompositions; liquid, solid and paste tooth and mouth detergents;laundry detergents and other textile agents including laundry blueing,bleaching, dyeing, softening, lubricating, and discharging compositions;depilatories; dust preventing compositions; fire extinguishingcompositions; drain, lavatory and radiator cleaners; antifreezing,anti-fogging, and anti-corrosion compositions; wood impregnants;electrolytic baths; etching compositions; cosmetics, shavingpreparations, shampoos and hair-wave lotions; tanning agents andfat-liquors for leather: photographic solutions; paint, stain and greaseremovers; dry-cleaning compositions; rug cleaners; petroleumvde-emulsifying compositions; fruit washing; fat splitting; preparationof dyes and dye intermediates; preparation of germicidal agents;preparation of resins and plasticizers such as the aliphatic substitutedphenol-aldehyde (formaldehyde), aliphatic substituted aryl sulphonamid,and aliphatic substituted aryl sulphonamid-aldehyde (formaldehyde) type:and any compositions requiring wetting, washing, emulsitying,penetrating, solubilizing, dispersing and like agents.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that the applicant does not limit himself to the specificproportions or embodiments thereof except as defined in the followingclaims.

I claim:

1. A process of preparing detergent aromatic sulphonic acid derivativeswhich comprises reactconsisting oi. olefine, halogen and hydroxyradicals and with a sulphonating agent, at least the sulphonationreaction being conducted while the organic material is dissolved in asolvent comprising liquid sulphur dioxide as the major constituent, andneutralizing the alkylated aromatic sulphonic acid product.

2. A process of preparing detergent aromatic sulphonic acid derivativeswhich comprises reacting in solution an aromatic compound with analiphatic compound containing at least six carbon atoms and with asulphonatlng agent, at least the sulphonation reaction being conductedwhile the organic material is dissolved in .a solvent comprising liquidsulphur dioxide as the major constituent, and neutralizing thealiphaticaromatic sulphonic acid product.

3. A process of preparing aromatic sulphonic acid derivatives whichcomprises simultaneously reacting an aromatic compound with an aliphaticcompound having at least six carbon atoms, and with a sulphonatingagent, the reactions being conducted while the organic material isdissolved in a solvent comprising liquid sulphur dioxide as the majorconstituent, and neutralizing the allphatic-aromatic sulphonic acidproduct.

4. A process of preparing detergent aromatic sulphonic acid derivativeswhich comprises reacting an aromatic compound with an aliphatic compoundcontaining at least six carbon atoms in the presence of a sulphuric acidderivative catalyst, and with a sulphonating agent, at least thesulphonation reaction being conducted while the organic material isdissolved with a solvent comprising liquid sulphur dioxide as the majorconstituent, and neutralizing the aliphatic-aromatic sulphonic acidproduct.

5. A process of preparing aromatic sulphonic acid derivatives whichcomprises reacting an aromatic compound with an aliphatic compoundcontaining at least six carbon atoms, in the presence of a sulphuricacid derivative catalyst, and with a sulphonating agent, the reactionsbeing conducted while the organic material is dissolved in a solventcomprising liquid sulphur dioxide as the major constituent, andneutralizing the aliphatic-aromatic sulphonic acid product.

6. A process of preparing detergent aromatic sulphonic acid derivativeswhich comprises reacting an aromatic compound with an aliphatic compoundcontaining at least six carbon atoms in the presence of an acid-reactingmetal halide catalyst, and then with a sulphonating agent, at least thesulphonation reaction being conducted while the organic material isdissolved in a solvent comprising liquid sulphur diox de as the majorconstituent, and neutralizing the aliphatic-aromatic sulphonic acidproduct.

7. A process of preparing aromatic sulphonic acid derivatives whichcomprises reacting an aromatic compound with an aliphatic compoundcontaining at least six carbon atoms. in the presence of anacid-reacting metal halide catalyst. and then with a sulphonating agent,the

reactions being conducted while the organic material is dissolved in asolvent comprising liquid sulphur dioxide as the major constituent, andneutralizing the aliphatic-aromatic sulphonic acid product.

8. The process of preparing aromatic sulphonic acid derivatives whichcomprises sulphonating an aliphatic substituted aromatic compound inwhich the aliphatic radical contains at least six carbon atoms whilesaid compound is dissolved in a solvent comprising liquid sulphurdioxide as the major constituent, and neutralizing thealiphatic-aromatic sulphonic acid product.

9. The process or preparing detergent aromatic sulphonic acidderivatives which comprises sulphonating an aliphatic substitutedaromatic compound in which the aliphatic radical contains at least sixcarbon atoms while said'compound is dissolved in a solvent consisting ofliquid sulphur dioxide and a stable low boiling point organic liquid,and neutralizing the aliphaticaromatic sulphonic acid product.

10. The process of preparing detergent aromatic sulphonic acidderivatives which comprises reacting an aromatic compound with anoleflnic compound containing at least six carbon atoms, and with asulphonating agent, the sulphonation reaction being conducted while theorganic material is dissolved in a solvent comprising liquid sulphurdioxide as the major constituent, and neutralizing thealiphatic-aromatic sulphonic acid product.

11. The process of preparing detergent aro-' matic sulphonic acidderivatives which comprises reacting an aromatic compound with ahalogencontaining aliphatic compound containing at least six carbonatoms and with a sulphonating agent, the sulphonation reaction beingconducted while the organic material is dissolved in a solventcomprising liquid sulphur dioxide as the major constituent, andneutralizing the aliphatic aromatic sulphonic acid product.

12. The process of preparing detergent aromatic sulphonic acidderivatives which comprises reacting an aromatic compound with analiphatic hydroxy compound containing at least six carbon atoms and witha sulphonating agent, the sulphonation reaction being conducted whilethe organic material is dissolved in a solvent comprising liquid sulphurdioxide as the major constituent, and neutralizing thealiphatic-aromatic sulphonic acid product.

13. The process of preparing detergent aromatic sulphonic acidderivatives which comprises reacting an aromatic hydrocarbon with analiphatic halide containing at least six carbon atoms, in the presenceof acid-reacting metal halide catalyst, and then with a sulphonatingagent, at least the sulphonation reaction being conducted while theorganic material is dissolved in a solvent comprising liquid sulphurdioxide as the major constituent, and neutralizing thealiphatic-aromatic sulphonic acid product. v

14. A process or preparing aromatic sulphonic acid derivatives whichcomprises reacting an aromatic hydrocarbon with an aliphatic hydroxycompound containing at least six carbon atoms, in the presence 01'sulphuric acid derivative catalyst, and with a sulphonating agent, thereactions sulphur dioxide as the major constituent, and

neutralizing the aliphatic-aromatic sulphonic acid product.

phonic acid derivatives which comprises react-- ing diphenyl with along-chain olefinic hydrocarbon containing at least six carbon atoms, inthe presence of a concentrated sulphuric acid and a solvent and thenwith a more concentrated sulphuric acid derivative while the diphenylderivative is dissolved in a solvent comprising liquid sulphur dioxideas the major portion constituent, and neutralizing thealiphatic-aromatic sulphonic acid product.

18. The continuous process of preparing aromatic sulphonic acidderivatives which comprises continuously mixing an aromatic compoundwith an aliphatic compound having at least six carbon atoms, and asolvent, continuously adding an alkylation catalyst to the mixture,after a suitable waiting period continuously adding a sulphonating agentand liquid sulphur dioxide to the reaction mixture, after asuitablewaiting period continuously adding water to the sulphonated product,continuously removing liquid sulphur dioxide from said dilute acidproduct, i

continuously washing the dilute acid product with a concentrated saltsolution in a countercurrent manner, and continuously bringing thewashed sulphonic acids into confluence with a concentrated alkali,suitably arranging the various cooling and heating steps to takeadvantage of heat interchange.

19. The process of preparing organic sulphonate detergents whichcomprises sulphonating an aliphatic substituted aromatic compound inwhich the aliphatic radical contains at least six carbon atoms withsulphur dioxide and chlorine gas in the presence of a solvent comprisingliquid sulphur dioxide as the major constituent, and reacting theresultant product with alkali to yield an organic sulphonate salt.

ROBERT LOUIS BRANDT.

